本文選題：Rh催化劑　切入點：氨基酸　出處：《齊齊哈爾大學》2017年碩士論文

【摘要】：現(xiàn)如今,過渡金屬在催化碳氫鍵活化的反應中被用來作為催化劑的研究越來越廣泛,在合成天然產(chǎn)物方面已經(jīng)取得了快速的發(fā)展,并且為功能分子合成的方法提供了高效直接的新途徑。尤其突出的是新型的三價銠催化劑,在C-H鍵活化構造C-C鍵、C-O鍵和C-N鍵的方面有很大的應用。此類催化劑不但有很高的催化活性同時在立體選擇性方面也有很大的優(yōu)勢,所以,利用新型的銠催化劑進行催化芳烴的研究受到科研人員的高度關注。本課題選取水楊醛和苯乙炔為實驗材料,利用含有不同氨基酸配體的銠催化劑催化氧化偶聯(lián)反應,合成了2-苯基-1,4-苯并哌喃酮。對不同氨基酸配體的新型銠催化劑進行合成與表征。并以Rh(cod)(L-Phe),Rh(cod)(L-Pro),Rh(cod)(L-Val),[Rh(cod)Cl]2,Rh(cod)(L-Ala)五種含有不同配體的Rh催化劑催化水楊醛與苯乙炔進行氧化偶聯(lián)反應。對比五種催化劑催化活性的高低,證明Rh(cod)(L-Phe)的催化活性最好。同時提出了銠催化劑的催化機理,由于Rh(cod)(L-Phe)中苯取代基團的存在,其Rh-N鍵易于斷裂與水楊醛形成中間體而促進反應的進行,令其催化效果達到最佳。利用紅外光譜(FT-IR)分析、核磁碳譜(13C-NMR)分析、核磁氫譜(1H-NMR)分析、元素分析以及氣相色譜分析(GC)對2-苯基-1,4-苯并哌喃酮進行表征,并確定其化學結(jié)構,測試結(jié)果顯示在銠催化劑的作用下首次合成了2-苯基-1,4-苯并哌喃酮。對目標產(chǎn)物2-苯基-1,4-苯并哌喃酮的合成產(chǎn)率的影響因素進行考察,優(yōu)化其工藝條件。對比等溫度、等時間的情況下2-苯基-1,4-苯并哌喃酮的收率,同時討論其催化活性,得到最優(yōu)催化方案為Rh(cod)(L-Phe)為催化劑在120℃的條件下油浴中反應5.5小時。
[Abstract]:Nowadays, transition metals have been widely used as catalysts in the catalytic reactions of hydrocarbon bond activation, and have made rapid progress in the synthesis of natural products.It also provides a new and efficient way for the synthesis of functional molecules.In particular, a new type of trivalent rhodium catalyst is widely used in C-H bond activation to form C-C bond, C-O bond and C-N bond.This kind of catalyst not only has high catalytic activity but also has a great advantage in stereoselectivity. Therefore the research of using new rhodium catalyst to catalyze aromatics is highly concerned by researchers.In this paper, salicylic aldehyde and phenylacetylene were used as experimental materials to synthesize 2-phenyl-4-benzoperazone by using rhodium catalyst with different amino acid ligands as catalyst for oxidative coupling reaction.New rhodium catalysts with different amino acid ligands were synthesized and characterized.Five Rh catalysts containing different ligands were used to catalyze the oxidative coupling of salicylic aldehydes with phenylacetylene.By comparing the catalytic activity of the five catalysts, it is proved that Rhcodanl-Phe) has the best catalytic activity.At the same time, the catalytic mechanism of rhodium catalyst was put forward. Because of the existence of benzene substituent group in Rhcodine L-Phe), the Rh-N bond of rhodium catalyst was easy to break down with salicylic aldehyde to form intermediate, which promoted the reaction, and the catalytic effect was the best.The chemical structures of 2-phenyl-1H-NMRs were characterized by FT-IR, 13C-NMRs, 1H-NMRs, elemental analysis and gas chromatographic analysis.The results showed that 2-phenyl-1-4-Benzooperazone was synthesized for the first time under the action of rhodium catalyst.The factors influencing the synthetic yield of the target product 2-phenyl-1 and 4-Benzooperazone were investigated and the technological conditions were optimized.Compared with the same temperature and time, the yield and catalytic activity of 2-phenyl -1n 4-Benzooperazone were discussed. The optimum catalyst was Rhcodcodonium L-Phe) for 5.5 hours in oil bath at 120 鈩，

本文編號：1729940